Azo-dyestuffs insensible in the dyebath towards hard water



Patented July 7, 1936 UNETED" STATES PATENT' OFF-ICE- AZO-DYESTUFFS INSENSIBLE IN THE DYEBATH TOWARDS HARD WATER Joseph Gyr and Otto Kaiser, Basel, Switzerland, assignors to firm Society of Chemicallndustry in Basle, Basel, Switzerland No Drawing. Original application December 10,

1932, Serial No. 646,707. Divided and this application'December 1, 1934,-Serial No. 755,634. In Switzerland December 17, 1931 2 Claims.

Serial No. 646,707 filed in the U. S. A. on December 10, 1932, and in Switzerland on December 17, 1931.

5 In U. S. Patent No. 1,667,312, Example 14, there is described a direct dyeing green polyazo-dyestuff, which can be made by the action ofthe diazotized azo-dyestufi from 1'-cliazo-8-hydroxy-- dyeing azo-dyestufis fast to light which, on the 25 one hand, are insensible in the dye-bath towards hard water, and on the other part, correspondto the general formula This is a division of our application for patent form of an O-acyl ester) and a middle component of the general formula z Q i (in which 11/, and x represent alkyl or alkoxy), 1

A mol.1-amino-8-hydroxynaphthalene-3,6-or 4,6-

disulfonic acid, 1 mol. cyanun'c chloride, 1 mol. of

a yellow'aminoazo-dyestufi and 1 mol. ammonia or 1 mol. of any amino-compound are caused to react with each othenand, if desired, the product 15 thus obtained is treated with a saponifying agent. The following example illustrates the invention the parts being .by weight Emample 621 parts of the dyestuff obtainable by coupling 1 mol. diazotized 1-amino-8-hydroxynaphthalene-4-toluenesulfonic acid-ester-4,6-disulfonic acid and 1 mol. 3-amino-4-cresolmethylether are diazotized and the product is introduced into a cooled ammoniacal solution or solution containing pyridine of 744 parts of the ternary conden- N= 0H N=N l v SOiNa- 40 S hNa 40 in which one .2 represents an SO3Na-gr0up and sation product from -1 mol. cyanuric chloride, 1 the other 2 a hydrogen atom, y and an alkyl or mol.1-amino-8-hydroxynaphthalene 3,6 disulalkoxy, R1 the radical of-ammonia or of an'amino ionic acid, 1 mol. 4-amino-4'-hydroxyazobenzenecompound and R2 the radical of a'yellow amino 3'-carboxylic acid and 1 mol aniline. When cou- 5 azo-dyestuff.

Such dyestuffs are obtained when, in known manner and in suitable sequence, 1 mol. of a diazotized azo-dyestufi from 1-diazo-8-hydroxynaphthalene-4,6-disulfonic acid (if desired in the pling is-complete; the whole is heated to 85 C. and at this temperature the toluene sulfonic acid residue is split ofi by addition of caustic soda solu tion. The dyestufi is worked up in the usual manner. It dyes cotton in hath made with either soft water or hard water full green tints. The

new dyestuff in the form of its sodium salt corresponds very probably with the formula OCH; CH HN-C N t l 300m 110 N=N N= I I I N= 011 CH: SO3N8 some 5 OINQ V The following table gives a number of further examples of dyestufis obtainable in accordance with the invention and. theirproperties:

Aniline 4 sulfonic acid Monomethylamine Diethylamine Monoethylaniline r 4,4 diamino diphenyl- 2,2-disulfonic acid '4 chloroaniline 3 sulfonic acid 3 amino ben zoic acid Aniline V 1 naphthylamine v 2 naphthyl-amine Aniline Monomethylarnine Initial component Middle component Condensation product of 1 mol. cyanuric chloride with 1 mol. each of- (1) 1 amino 8 hyl methyl 3 amino 1 amino 8 hydroxynaph- 4 amino 4' hydroxyazodrox'ynaphtha- 4 methoxybenzene thalene 3,6 disulfonlc benzene 3' carboxyllc lene 4,6 disulacid acld i'om'o acid. (2) Do do do do (3) Do .do .do. do (4) Dodo do- .do. (5) D do. do- .do

(6) Do do 7 do- .do (7) Dodo do do (8) Dododo 4 amino 3 methoxyazo benzene 3 snlionic acid (9) i Do do do 0-- I (10) I Do do---" 1 ammo 8 hydroxynaph 4 amino 4 hydroxyazo thalene 4,6 disulionic benzene 3 carboxylic acid 1 acid. (11) Do 1 4 dimethyl 2 am 1- amino 8- hydroigynaph do V inobenzene thaene 3,6 disulfonic 7 aci (12) Do 1, 4 dimethoxy 2 do.

aminobenzene.

The formulas of some of the dyestuffs oi: the above table are as follows:- No. 3

' can, no N: N=N

NaOzS OaNa f 1 1 /NO\ a mm no I?O /N i EN N=,N

on; NaO;S SOaNa OCH; OaNa SOaNa ITO No. 11 and R4 stand for radicals of the benzene series,

HN -k cm H N-O N 5 N=C H0 N=N N=N I G HNC N=NC OH CH: Na0;S SO Na COOH NBOIS OaNa which products constitute dark powders, are solu- No. 12 ble in water to green solutions, and dye cotton (3H1 N-G IOCHI HO HNG/ N COON Q 8 HO N=N N==N l OOH: N80: SOJNa News SOaNa or regenerated cellulose in green tints which are fast to light.

2. The green, direct dyeing azo-dyestufi fast to light which is insensible in the dyebath to- What we claim is:-

l. The green direct dyeing azo-dyestufis fast to light which are insensible in the dyebath towards hard water and correspond to the general formula /N-C\ B: 1 H0 HN-C/ \N l N=C H0 N=N N=N I i III-Rr-N=NR y SOzNa z E SOuNa z SOaNfl in which one 2 represents an SOaNa-group and wards hard water and corresponds to the forthe other 2 represents a hydrogen atom, 11 and a: mula H '0 /N N-O 0cm H0 HN-C N l GOONa N=C E0 N=N N=N- cm B08N8- SOzNa H S0;Na

SOaNa which product constitutes a dark powder, is soluble in water to a green solution, and dyes cotton or regenerated cellulose green tints which are fast to light.

represent a substituent selected from the group consisting of alkyl and alkoxy, R1 stands for .a member of the class consisting of hydrogen and alkyl, R2 stands for a member of the class consisting of hydrogen, alkyl and aryl radicals of the benzene or naphthalene series, and R3 JOSEPH GYR.

OTTO KAISER. 7 0 

